EP0436076A2 - Polymermischung, enthaltend einen Polyester und ein die Schlagzähigkeit verbessernden Zusatz - Google Patents
Polymermischung, enthaltend einen Polyester und ein die Schlagzähigkeit verbessernden Zusatz Download PDFInfo
- Publication number
- EP0436076A2 EP0436076A2 EP90119364A EP90119364A EP0436076A2 EP 0436076 A2 EP0436076 A2 EP 0436076A2 EP 90119364 A EP90119364 A EP 90119364A EP 90119364 A EP90119364 A EP 90119364A EP 0436076 A2 EP0436076 A2 EP 0436076A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- polymer mixture
- rubber
- units derived
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 229920002959 polymer blend Polymers 0.000 title claims abstract description 35
- 229920000728 polyester Polymers 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- -1 poly(styrene-butadiene) Polymers 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 239000005060 rubber Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the invention relates to a polymer mixture which comprises (A) a polyester built up from units derived from an alkanediol and an aromatic dicarboxylic acid, (B) an agent to improve the impact strength built up from a rubber-like backbone on which a vinylaromatic monomer and an alkylmethacrylate have been grafted, and (C) conventionally used additives.
- the invention also relates to articles formed from the polymer mixture according to the invention.
- Polymer mixtures which comprise a polyester and an agent to improve the impact strength of the type mentioned hereinbefore are known per se .
- an agent used to improve the impact strength is an MMBS-grafted core-shell interpolymer which is commercially available as ACRYLOID ® KM 653.
- This known agent consists for approximately 80% by weight of a rubber-like backbone on which methylmethacrylate and styrene have been grafted in a weight ratio of approximately 1.5 : 1.
- EP-A-0187313 describes polyester compositions comprising 52-99 parts by weight of at least one polyalkylene terephtalate and 1-48 parts by weight of a graft polymer.
- Said graft polymer has been obtained by grafting 10-30% by weight of monomer(s) on 70-90% by weight of a rubbery graft base.
- the graft polymer comprises 80% by weight of the rubbery graft base.
- the low temperature impact strength of the known composition at -40°C is less than 50% of the corresponding value at 23°C (example I).
- FR-A-2320968 describes blends of an amorphous polyester and a graft polymer.
- the graft polymer may comprise 90-40 parts by weight of a diene upon which have been grafted 10-60 parts by weight of monomers. In the examples the maximum amount of diene rubber is 75 parts by weight.
- the polymer mixture according to the invention is characterised in that constituent (B), i.e. the agent to improve the impact strength, consists for 86-90%, exclusive 90% by weight of the rubber-like backbone.
- constituent (B) having a rubber-like backbone built up from polybutadiene or a poly(styrene-butadiene) having more than 80% by weight of butadiene units.
- constituent (B) is composed so as the consist of 86-90%, exclusive 90%, by weight of the rubber-like backbone, 8-12% by weight of units derived from the alkylmethacrylate and 2-6% by weight of units derived from a vinylaromatic monomer, or even more preferably of 88% by weight of a polybutadiene backbone, 6-10% by weight of units derived from methylmethacrylate and 2-6% by weight of units derived from styrene.
- the polymer mixture according to the invention preferably comprises 50-80% by weight of constituent (A), 20-50% by weight of constituent (B), all this calculated with respect to the sum of the parts by weight of (A) plus (B).
- the polymer mixture according to the invention comprises at any rate the following constituents:
- the polymer mixture according to the invention may moreover comprise one or more conventionally used additives (C).
- the invention relates to polymer mixtures which comprise a polyester having units derived from an alkanediol and an aromatic dicarboxylic acid.
- the polyester may comprise units derived from one or more alkanediol compounds.
- the polyester may also comprise units derived from one or more aromatic dicarboxylic acids.
- the polyester may comprise units derived from one or more other diol compounds or polyol compounds.
- the polyester generally comprises an excess of units derived from an alkanediol with respect to the optionally present units derived from other diol compounds or polyol compounds. Examples of suitable alkanediol compounds are ethanediol or butane-1,4-diol.
- the polyester may also comprise units derived from other dicarboxylic acids or polycarboxylic acids.
- the greater part of the units derived from carboxylic acids is derived from an aromatic dicarboxylic acid.
- Suitable aromatic dicarboxylic acids are terephthalic acid and isophthalic acid.
- a polyester is preferably used a polyester having more than 70 mol% of units derived from terephthalic acid and butane-1,4-diol. It is also possible to use a mixture of one or more different polyesters, for example, a mixture of polyethylene terephthalate.
- the polymer mixture according to the invention comprises as an agent to improve the impact strength an agent which is built up from a rubber-like backbone on which a vinylaromatic monomer and an alkylmethacrylate have been grafted.
- the preparation of such agents is known per se ; for this purpose reference may be made, for example, to US-A-3,985,704 and US-A-4,180,494.
- These agents are generally prepared starting from a rubber-like latex.
- the monomers are grafted on the rubber particles; sometimes in a single step, sometimes in several steps. It is also possible to graft small quantities of cross-linking agents and graft-linking agents together with the monomers on the rubber-like latex particles.
- the content of the rubber-like backbone in the agent is between 86-90%, exclusive 90%, by weight. With a content of less than 86% by weight the agent is less effective to improve the impact strength at low temperatures. In practice it is difficult to prepare agents having a rubber content of 90% or more by weight.
- the rubber-like backbone preferably consists of polybutadiene or a poly(styrene-butadiene) having more than 80% by weight of butadiene. Preferably 8-12% by weight of alkyl methacrylate units and 2-6% by weight of units of a vinylaromatic monomer are grafted on the rubber-like backbone. Styrene may be used as a vinylaromatic monomer.
- a suitable alkylmethacrylate is methylmethacrylate or ethylmethacrylate.
- the polymer mixture according to the invention may comprise one or more conventionally used additives, for example, stabilisers, pigments, dyes and mould-release agents.
- the polymer mixture according to the invention can be obtained according to the conventional methods of preparing polymer mixtures, for example, by melt extrusion.
- polymer mixtures Three polymer mixtures were prepared: prior art polymer mixtures A and B and polymer composition I according to the invention.
- the polymer mixtures were prepared by mixing the following constituents in a double-blade extruder:
- Test rods were manufactured from the resulting polymer mixtures by injection moulding to determine the Izod notched impact strength. The results obtained, measured at different temperatures, are also recorded in Table A hereinafter. The computed rubber content of each polymer mixture is also recorded in the Table.
- polymer mixture according to the invention has a better impact strength at low temperatures. This cannot be explained on the basis of a possibly higher rubber content in the polymer mixture when the same quantity of the agent to improve the impact strength is used.
- Polymer mixture I according to the invention having a comparable rubber content as polymer mixture A has a much more favourable transition temperature for the ductile to brittle fracture.
- Comparative polymer mixtures A and B having the same agent to improve the impact strength in two different quantities and hence with a different rubber content in the polymer mixture have substantially the same transition temperature.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8903169 | 1989-12-28 | ||
| NL8903169A NL8903169A (nl) | 1989-12-28 | 1989-12-28 | Polymeermengsel dat een polyester en een middel voor het verbeteren van de slagsterkte bevat. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0436076A2 true EP0436076A2 (de) | 1991-07-10 |
| EP0436076A3 EP0436076A3 (en) | 1992-03-18 |
Family
ID=19855837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19900119364 Ceased EP0436076A3 (en) | 1989-12-28 | 1990-10-09 | Polymer mixture which comprises a polyester and an agent to improve the impact strength |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0436076A3 (de) |
| NL (1) | NL8903169A (de) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1062390A (en) * | 1975-08-11 | 1979-09-11 | William Steffancin | Amorphous polyester graft polymer alloys |
| JPS62187759A (ja) * | 1984-10-31 | 1987-08-17 | ヘキスト・セラニーズ・コーポレーション | 衝撃挙動にすぐれた新規熱可塑性ポリエステル組成物 |
| DE3446225A1 (de) * | 1984-12-19 | 1986-06-19 | Basf Ag, 6700 Ludwigshafen | Schlagzaehe, thermoplastische polyesterformmassen |
-
1989
- 1989-12-28 NL NL8903169A patent/NL8903169A/nl not_active Application Discontinuation
-
1990
- 1990-10-09 EP EP19900119364 patent/EP0436076A3/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| NL8903169A (nl) | 1991-07-16 |
| EP0436076A3 (en) | 1992-03-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19901009 |
|
| AK | Designated contracting states |
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| PUAL | Search report despatched |
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| AK | Designated contracting states |
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| 17Q | First examination report despatched |
Effective date: 19940629 |
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| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
| 18R | Application refused |
Effective date: 19941217 |